CN102010565A - Method for preparing ablative resistance resin - Google Patents
Method for preparing ablative resistance resin Download PDFInfo
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- CN102010565A CN102010565A CN 201010531803 CN201010531803A CN102010565A CN 102010565 A CN102010565 A CN 102010565A CN 201010531803 CN201010531803 CN 201010531803 CN 201010531803 A CN201010531803 A CN 201010531803A CN 102010565 A CN102010565 A CN 102010565A
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Abstract
The invention discloses a method for preparing ablative resistance resin which is a compound of hyperbranched polyborate ester resin and high-temperature resistance thermosetting resin. The hyperbranched polyborate ester is a hyperbranched polymer which contains boron, is provided with a rigid skeleton and is synthesized by condensation reaction of a boron-containing compound and polyatomic alcohol or polyatomic phenol; and the hyperbranched molecular structure and excellent heat resistance of the polymer are utilized so that the polymer and the high-temperature resistance thermosetting resin are compounded, thus the heat resistance, mechanical property and processing manufacturability of resin can be simultaneously improved. The ablative resistance resin obtained by the method has the advantages of high carbon residue rate, excellent mechanical property and ablative resistance, is easy to process, and can be used for preparing ablative resistance materials, carbon materials, anti-friction materials and the like.
Description
Technical field
The present invention relates to a kind of preparation method of thermosetting resin, be specifically related to a kind of method for preparing the resin of anti-the ablation by hyperbranched poly boric acid ester resin and high temperature resistant thermosetting resin compounded.
Background technology
At space industry, the exploitation of aircraft thermally protective materials is an important research project always.The aerospacecraft work under bad environment works long hours under high heat-flux conditions for guaranteeing it, need take effective thermal protection measure.Chemistry such as the ablation method is the most also to be most widely used a kind of anti-by the use of thermal means at present, decomposition, depolymerization, fusing, evaporation, gasification and the ionization of this method by material and physical process are removed a large amount of heats, reach the solar heat protection purpose.Present widely used ablator is to be the matrix material of matrix with the thermosetting resin, this polymer matrix composites have high temperature resistantly, anti-wash away, heat conduction and excellent properties such as thermal expansivity is little, specific tenacity and specific rigidity height, the good and anti-width of cloth of fatigue resistance are penetrated, can satisfy the requirement of ablating heat shield material preferably.
Comparatively the resin matrix of anti-ablative composite material commonly used mainly contains ammonia resol, ba phenolic resin, phosphorous-containing phenolic resin, boron bakelite resin, benzoxazine colophony, phenol cyanate resin and poly-aryl ethane resin etc. at present.Wherein, resol such as ammonia phenolic aldehyde, barium phenolic aldehyde, phosphorus phenolic aldehyde and boron phenolic aldehyde have favorable mechanical performance and resistance toheat, and raw material is easy to get, and are synthetic convenient, of a great variety, play an important role in ablation resistant material and field of novel carbon material.But the shortcoming of these resol also clearly, and the temperature and pressure relatively poor except toughness, that the curing molding process need is higher, when they were used as ablation resistant material and carbon material precursor, its heat decomposition temperature and carbon yield also had much room for improvement.Discharge a large amount of micromolecular shortcomings during at phenolic resin curing, people have developed open loop curing thermosetting resin, as benzoxazine colophony and phenol cyanate resin, these resins have the chemical structure close with resol, suitable thermotolerance, better manufacturability and mechanical property, but its thermotolerance and toughness can not satisfy the demand for development of ablation resistant material and carbon material equally.Poly-aryl ethane resin is a class aromatics phenylene polymkeric substance that is polymerized by polyacetylene base aromatic monomer, has extraordinary thermostability, and theoretical carbon residue rate is up to 90%, and no small molecules is overflowed in the solidification process.Yet, contain a large amount of aromatic rings in the poly-aryl ethane molecule, cause the interfacial bond property extreme difference between toughness, resin and the fortifying fibre of resin.In addition, poly-aryl ethane resin solidification exothermic heat of reaction amount is big, implode easily, and whole solidification process complex process and be difficult to control is for the preparation of matrix material brings inconvenience.Cost is too high also to be an obstacle of poly-aryl ethane resin widespread use.
Relatively poor at the existing ubiquitous toughness of high temperature resistant thermosetting resin, manufacturability is not good, the resistance toheat defective that has much room for improvement of carbon residue rate especially, investigators have proposed multiple method of modifying about this resinoid, but these traditional method of modifying mostly are difficult to the contradiction between mediation resin thermotolerance, manufacturability and the toughness.Therefore, press for and take new modified method, mechanical property, thermotolerance and the manufacturability of this class thermosetting resin are promoted comprehensively.Hyperbranched polymer highly branched, that have a large amount of active end groups has that solvability is good, viscosity is low and the reactive behavior advantages of higher, is widely used in the thermosetting resin toughening modifying.Existing studies show that, hyperbranched polymer can guarantee thermosetting resin toughness, modulus and thermotolerance to a certain extent.Obtain high performance thermosetting resin, promptly in toughness reinforcing, modulus, thermotolerance and manufacturability are also significantly improved, then require us to select for use high temperature resistant hyperbranched polymer to come with thermosetting resin compound with special construction.
Hyperbranched poly boric acid ester resin (patent of invention ZL 200710017753.3) has the rigid backbone of boracic and a large amount of active end groups, itself and thermosetting resin is compound, can be when improving thermosetting resin thermostability and carbon yield, improve the manufacturability and the mechanical property of resin, make a kind of resin of anti-ablation of high comprehensive performance.This resin of anti-the ablation not only can replace the resin of anti-ablation the commonly used at present, and can be used for fields such as carbon material and high-abrasive material, gives full play to its high carbon yield, high-modulus and excellent advantages such as mechanical property.
Summary of the invention
The preparation method who the purpose of this invention is to provide the simple resin of anti-ablation of a kind of preparation technology.
For achieving the above object, technical scheme provided by the invention is:
1) press mass fraction with 5～30 parts hyperbranched poly boric acid ester resin dissolves in 50 parts intensive polar solvent;
2) press mass fraction with 50～100 parts high temperature resistant thermosetting resin dissolves in 100 parts organic solvent;
3) under 20～90 ℃, above-mentioned hyperbranched poly boric acid ester resin solution is mixed with the mass ratio of high temperature resistant thermosetting resin solution by 1: 1, stir and obtained the resin solution of anti-ablation that mixes in 10～60 minutes.
High temperature resistant thermosetting resin of the present invention is one or more in ammonia resol, ba phenolic resin, phosphorous-containing phenolic resin, molybdenum resol, boron bakelite resin, benzoxazine colophony, phenol cyanate resin and the poly-aryl ethane resin;
Intensive polar solvent is N, a kind of in dinethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO) or the N-N-methyl-2-2-pyrrolidone N-;
Organic solvent is a kind of in acetone, ethanol, toluene, dimethylbenzene or the dioxane.
Compare with other high temperature resistant thermosetting resin, the gained resin of anti-ablation of the present invention has following advantage: (1). and the carbon residue rate of this resin (800 ℃, nitrogen atmosphere) has improved 7～10 percentage points; (2). this resin has good curing process, and its curing initiation temperature, cure peak temperature and curing exotherm amount all reduce; (3). glass fibre or the carbon fiber reinforced resin composite materials of anti-ablation the and the high temperature resistant thermosetting polymer matrix composites ratio of not introducing hyperbranched poly boric acid ester resin accordingly, the former flexural strength and interlaminar shear strength have improved 20～25% than the latter, and modulus in flexure has improved 5～10%; (4). the ablation resistance of glass fibre or the carbon fiber reinforced resin composite materials of anti-the ablation also is better than not introducing accordingly the high temperature resistant thermosetting polymer matrix composites of hyperbranched poly boric acid ester resin; (5). this resin of anti-the ablation has excellent thermotolerance, mechanical property and processing technology, can be used for preparing ablation resistant material, carbon material and high-abrasive material etc.
Embodiment
Embodiment 1:1) at first, press mass fraction with 30 parts hyperbranched poly boric acid ester resin dissolves in 50 parts intensive polar solvent N, in the dinethylformamide;
2) secondly, 100 parts high temperature resistant thermosetting resin ammonia resol is dissolved in 100 parts the organic solvent-acetone by mass fraction;
3) last, under 25 ℃, above-mentioned hyperbranched poly boric acid ester resin solution is mixed with the mass ratio of high temperature resistant thermosetting resin solution by 1: 1, stir and obtained the resin solution of anti-ablation that mixes in 15 minutes.
Embodiment 2:1) at first, press mass fraction with 10 parts hyperbranched poly boric acid ester resin dissolves in 50 parts intensive polar solvent N-N-methyl-2-2-pyrrolidone N-;
2) secondly, 70 parts high temperature resistant thermosetting resin ba phenolic resin is dissolved in 100 parts the organic solvent ethanol by mass fraction;
3) last, under 50 ℃, above-mentioned hyperbranched poly boric acid ester resin solution is mixed with the mass ratio of high temperature resistant thermosetting resin solution by 1: 1, stir and obtained the resin solution of anti-ablation that mixes in 10 minutes.
Embodiment 3:1) at first, press mass fraction with 5 parts hyperbranched poly boric acid ester resin dissolves in 50 parts intensive polar solvent dimethyl sulfoxide (DMSO);
2) secondly, 50 parts high temperature resistant thermosetting resin phosphorous-containing phenolic resin is dissolved in 100 parts the organic solvent toluene by mass fraction;
3) last, under 90 ℃, above-mentioned hyperbranched poly boric acid ester resin solution is mixed with the mass ratio of high temperature resistant thermosetting resin solution by 1: 1, stir and obtained the resin solution of anti-ablation that mixes in 30 minutes.
Embodiment 4:1) at first, press mass fraction with 20 parts hyperbranched poly boric acid ester resin dissolves in 50 parts intensive polar solvent N,N-dimethylacetamide;
2) secondly, 90 parts high temperature resistant thermosetting resin molybdenum resol is dissolved in 100 parts the organic solvent dimethylbenzene by mass fraction;
3) last, under 20 ℃, above-mentioned hyperbranched poly boric acid ester resin solution is mixed with the mass ratio of high temperature resistant thermosetting resin solution by 1: 1, stir and obtained the resin solution of anti-ablation that mixes in 50 minutes.
Embodiment 5:1) at first, press mass fraction with 25 parts hyperbranched poly boric acid ester resin dissolves in 50 parts intensive polar solvent N, in the dinethylformamide;
2) secondly, by mass fraction 50 parts high temperature resistant thermosetting resin ammonia resol is dissolved in 100 parts the organic solvent-acetone, again 80 parts of benzoxazine colophonies is dissolved in 100 parts the organic solvent-acetone;
3) last, under 70 ℃, above-mentioned hyperbranched poly boric acid ester resin solution is mixed by 1: 0.2: 0.8 mass ratio with ammonia phenol resin solution, benzoxazine colophony solution, stir and obtained the resin solution of anti-ablation that mixes in 60 minutes.
Embodiment 6:1) at first, press mass fraction with 15 parts hyperbranched poly boric acid ester resin dissolves in 50 parts intensive polar solvent N-N-methyl-2-2-pyrrolidone N-;
2) secondly, by mass fraction 70 parts high temperature resistant thermosetting resin benzoxazine colophony is dissolved in 100 parts the organic solvent dioxane, 50 parts phenol cyanate resin is dissolved in 100 parts the organic solvent dioxane, 100 parts poly-aryl ethane resin dissolves is in 100 parts organic solvent dioxane;
3) last, under 40 ℃, with above-mentioned hyperbranched poly boric acid ester resin solution and benzoxazine colophony solution, phenol cyanate resin solution, poly-aryl ethane resin solution by 1: 0.3: 0.4: 0.3 mass ratio mixes, and stirs to obtain the resin solution of anti-ablation that mixes in 40 minutes.
Claims (4)
1. the preparation method of the resin of anti-the ablation is characterized in that:
1) at first, press mass fraction with 5～30 parts hyperbranched poly boric acid ester resin dissolves in 50 parts intensive polar solvent;
2) secondly, press mass fraction with 50～100 parts high temperature resistant thermosetting resin dissolves in 100 parts organic solvent;
3) last, under 20～90 ℃, above-mentioned hyperbranched poly boric acid ester resin solution is mixed with the mass ratio of high temperature resistant thermosetting resin solution by 1: 1, stir and obtained the resin solution of anti-ablation that mixes in 10～60 minutes.
2. the preparation method of the resin of anti-ablation the according to claim 1 is characterized in that: described high temperature resistant thermosetting resin is one or more in ammonia resol, ba phenolic resin, phosphorous-containing phenolic resin, molybdenum resol, boron bakelite resin, benzoxazine colophony, phenol cyanate resin and the poly-aryl ethane resin.
3. the preparation method of the resin of anti-ablation the according to claim 1 is characterized in that: described intensive polar solvent is N, a kind of in dinethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO) or the N-N-methyl-2-2-pyrrolidone N-.
4. the preparation method of the resin of anti-ablation the according to claim 1 is characterized in that: described organic solvent is a kind of in acetone, ethanol, toluene, dimethylbenzene or the dioxane.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102492260A (en) * | 2011-11-29 | 2012-06-13 | 广东榕泰实业股份有限公司 | Ablation-resisting composite material resin composition and preparation method of ablation-resisting composite material |
| CN102660102A (en) * | 2012-05-02 | 2012-09-12 | 江苏亚邦新材料科技有限公司 | Method for preparing high-temperature resistant insulating resin and application thereof |
| CN104774424A (en) * | 2015-04-23 | 2015-07-15 | 西安交通大学 | Ablation-resistance resin for resin film infusion process and preparation method thereof |
| CN105647108A (en) * | 2016-03-30 | 2016-06-08 | 西安交通大学 | Siloxane-modified phenolic resin for hot melt preimpregnation technology and preparation method of siloxane-modified phenolic resin for hot melt preimpregnation technology |
| CN109486104A (en) * | 2018-10-31 | 2019-03-19 | 西安长峰机电研究所 | A kind of benzoxazine resin base reinforcing fiber composite material and its forming method |
| CN110499000A (en) * | 2019-08-16 | 2019-11-26 | 西安长峰机电研究所 | A kind of resistance to ablation of benzoxazine resin base, heat-insulation composite material and its forming method |
| CN111234459A (en) * | 2020-01-14 | 2020-06-05 | 山东德钧智能科技服务有限公司 | Modified resin, composite material and heat protection plate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101041718A (en) * | 2007-04-27 | 2007-09-26 | 西安交通大学 | Preparation method for hyper branched boric acid ester |
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2010
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101041718A (en) * | 2007-04-27 | 2007-09-26 | 西安交通大学 | Preparation method for hyper branched boric acid ester |
Non-Patent Citations (2)
| Title |
|---|
| 《CARBON》 20070619 Yuhong Liu et al Pyrolysis and structure of hyperbranched polyborate modified phenolic resins , 2 * |
| 《宇航材料工艺》 20091231 许培俊 等 硼化物改性酚醛树脂研究进展 , 第6期 2 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102492260A (en) * | 2011-11-29 | 2012-06-13 | 广东榕泰实业股份有限公司 | Ablation-resisting composite material resin composition and preparation method of ablation-resisting composite material |
| CN102492260B (en) * | 2011-11-29 | 2013-07-31 | 广东榕泰实业股份有限公司 | Ablation-resisting composite material resin composition and preparation method of ablation-resisting composite material |
| CN102660102A (en) * | 2012-05-02 | 2012-09-12 | 江苏亚邦新材料科技有限公司 | Method for preparing high-temperature resistant insulating resin and application thereof |
| CN104774424A (en) * | 2015-04-23 | 2015-07-15 | 西安交通大学 | Ablation-resistance resin for resin film infusion process and preparation method thereof |
| CN104774424B (en) * | 2015-04-23 | 2017-04-26 | 西安交通大学 | Ablation-resistance resin for resin film infusion process and preparation method thereof |
| CN105647108A (en) * | 2016-03-30 | 2016-06-08 | 西安交通大学 | Siloxane-modified phenolic resin for hot melt preimpregnation technology and preparation method of siloxane-modified phenolic resin for hot melt preimpregnation technology |
| CN109486104A (en) * | 2018-10-31 | 2019-03-19 | 西安长峰机电研究所 | A kind of benzoxazine resin base reinforcing fiber composite material and its forming method |
| CN110499000A (en) * | 2019-08-16 | 2019-11-26 | 西安长峰机电研究所 | A kind of resistance to ablation of benzoxazine resin base, heat-insulation composite material and its forming method |
| CN111234459A (en) * | 2020-01-14 | 2020-06-05 | 山东德钧智能科技服务有限公司 | Modified resin, composite material and heat protection plate |
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| CN102010565B (en) | 2013-03-13 |
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Effective date of registration: 20211221 Address after: 313100 Chengnan Industrial Park, Heping Town, Changxing County, Huzhou City, Zhejiang Province Patentee after: Zhejiang Shitao Dingge New Material Co.,Ltd. Address before: 710049 No. 28 West Xianning Road, Shaanxi, Xi'an Patentee before: XI'AN JIAOTONG University |
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